Alkoxyderivatives of 1-aminonaphthalene-8-carboxylic-acid anhydride and process of making same



Patented Oct. 21, 1930 UNITEQSTATES nionlmn 13E132; useums, F FnANxFoR'LoN-TnE-MAIN, GERMANY,

PATENT oFF-icE,--,

Ass'IG oRs T0 GENERAL ANILINE wonxs, me, on NEW onx, N. Y., A CORPORA- Mon '01" nrmawn'nn If i nnxoxxnnmvn'r xvns or i-nmmonnrnrnnmmn-s-oAnBoxYmc-Acm ANHYDRIDE mnrnoenss or Maxine same in Drawing, original application filed November 29, 1926,8eria1 no..1s-1,59e, and in Germany December 4,

- I 1925, Ilivided and this application filed November 17, 1927. Serial No. 284,036.

Thisapplication.is a division ofour application Serial 'No; 151,596, filed November 29, 1926, which has matured into PatentfNo.

1,728,995, dated "Se'ptJ24, 1929;

a In the parent application h'ydroxy derivatives Off the 1'-aminoaa-phthalene-8-carboxylic acid-anhydride ('naphthostyril) are described.

Our present divisional application relates to new alkoxy derivatives of l-aminonaph thalene-8-carboxylic-acid-anhydride corresponding probably to the general formula:

2 aminonaphthalene 8 carboxylic acid by treatment'with alkaline saponifying agents.

In order to further illustrate our invention the following example is given, the parts being by Weight and all temperatures in centigrade degrees, but it is understood that our invention is not limited to the particular products or reaction conditions mentioned thereinz v Example 1 part of the sodium salt of 5-hydroxynaphthostyril (of. Example 4 of the parent application) is mixed with 47133115 ofthe methylic-es ter of paratoluene-solfonic acid,

'40 4 parts of sodium-carbonate and about parts of trichlorobenzene and the mixture is heated to about -17 0, until a sample no longer combines with a diazo compound. Then the trichlorobenzene is driven off by 45 steam and the residue is filtered, Washed and dried. The b-methoxynaphthostyril thus' obtained having probably the formula:

a t- Z s melts, when (crystallized from" benzene, at 223. By boiling it witha caustic soda solution of'about. 10% it is saponifiedto the 01 responding 5,-methox-y-l-aminonaphthalene; S-carboxylic acid of thejprobable formula;

OCH; The free acid, obtainable by gently acidifying and cooling the above solution, is when dry, at colorlessrpow der easily soluble in alkalies, it is diazotizztblfiand capable of combining with diazocompounds. 1y soluble diazooompound crystallizes in yellow crystals and yields azodyestufis, when combined with hydroxyor aminocompounds.

;:By, :warming the '5methoxy-1-.amino-- n'aphth'alene-8 carboxylicacid with acids the 5.-methoxynaphthostyril is. I -obtained. In a similar way by ethylatf-ing the 5-hydroxyn aphthostyrilin the usual manner for instance with ethylbroinide' the corresponding 5-ethoxynaphthostyril is obtained, melting at about 200 and showing the same characteristic properties as the methylderivativeQ By treating 1 6hydroxynaphthostyril of. Example 2 of" the parentQapplication) with 7 suitable alkylating agents it isalkyila-ted in the hydroxy-g roup and the thus formed G-alkoxynaphthostyrils can be saponified to the-cm;-

responding G-alkoxy-1-aminonaphthalene-8- carboxylic acids. In the same manner 3- hydroxynapthostyril can be converted into 3-alkoxynaphthostyrils.

We claim:

1. A process for manufacturing alkoxy derivatives of 1-aminonaphthalene-S-carboxylic-acid-anhydride corresponding probably to the general formula:

which process comprises treating hydroxy derivatives of 1-aminonaphthalene-8-ca-rboxylic-acid-anhydride with an alkylating agent. 2. As new products the compounds of the general formula:

wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group CO-NH, being in the .alkyl wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group CONH, being in the form of the anhydride crystalline powders neither diazotizable nor capable of combining with diazo compounds, being converted by treatment with alakline saponifying agents into the corresponding alkoxy derivatives of 1-aminonaphthalene-S-carboxylic acid which are, when dry, colorless powders easily soluble in alkalies, being diazotizable and capable of combining with diazo compounds.

4. As a new product the compound of the general formula:

wherein Y represents an amino group and Z a carboxylic acid group, or Y and Z jointly represent the group CONH, being in the form of the anhydrid e a crystalline powder neither diazotizable nor capable of combining with diazo compounds, being converted by treatment with alkaline saponifying agents into the corresponding methoxy derivative of l-aminonaphthalene-8-carboxylic acid which is, when dry a colorless powder easily soluble in alkalies, being diazotizable and capable of combining with diazo compounds.

In testimony whereof, we aflix our signatures.

RICHARD HERZ. FRITZ SGHULTE. 

